Room-Temperature Arylation of Arenes and Heteroarenes with Diaryl­iodonium Salts by Photoredox Catalysis

Abstract

Aryl radicals produced by irradiation of diaryliodonium salts with visible light under the catalysis of [Ru(bpy)₃]²⁺ undergo coupling with a wide range of arenes and heteroarenes, affording various biaryls through direct C–H arylation at room temperature.

Key words

arenes - heteroarenes - visible light - aryl radicals - ruthenium

• References and Notes

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• 16 General Procedure for the Direct Arylation of Arenes and Heteroarenes with Diaryliodonium Salts Method AA flame dried 10 mL Schlenk tube was equipped with a rubber septum and magnetic stir bar and was charged with tris(2,2′-bipyridyl)ruthenium(II) chloride hexahydrate (3 mg, 0.004 mmol, 0.01 equiv), diarylionium salts (0.4 mmol, 1.0 equiv), arenes or heteroarenes (20 mmol, 50 equiv), and MeCN (3 mL). The mixture was degassed by the freeze-pump-thaw procedure with Ar, and then the Schlenk tube was placed at a distance of 10 cm from a 3w Blue LED bulb. After stirring at 25 °C for 12 h, the solvent was removed under reduced pressure, and the residue purified by flash chromatography to afford the product. The identity and purity of the product was confirmed by ¹H NMR and ¹³C NMR spectroscopy and MS or HRMS.Method BThis method is the same as method A except that a smaller amount of arene or heteroarene (4 mmol, 10 equiv) was used. The method was used mainly for substrates that did not fully dissolve under the conditions in method A.1-Methyl-2-Phenyl-1H-pyrrole (3a)Compound 3a was obtained following the method A. White solid, mp 43–44 °C; R_f  = 0.2 (PE–CH₂Cl₂ = 10:1); yield 87% (63 mg). ¹H NMR (400 MHz, CDCl₃): δ = 7.43–7.40 (m, 4 H), 7.34–7.31 (m, 1 H), 6.75 (s, 1 H), 6.27–6.24 (m, 2 H), 3.69 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 134.7, 133.5, 128.8, 128.4, 126.7, 123.7, 108.7, 107.8, 35.1. MS (EI): m/z = 158.1 [M + H]⁺.1-Methyl-2-(4-Fluorophenyl)-1H-pyrrole (3b)Compound 3b was obtained following the method A. White solid, mp 64 °C; R_f  = 0.2 (PE–CH₂Cl₂ = 20:1); yield 91% (64 mg). ¹H NMR (400 MHz, CDCl₃): δ = 7.39–7.36 (m, 2 H), 7.13–7.09 (m, 2 H), 6.73 (d, J = 2.0, 1 H), 6.23–6.22 (m, 2 H), 3.65 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 162.0 (d, J _C–F = 245.8 Hz), 133.6, 130.3 (d, J _C–F = 8.8 Hz), 129.5 (d, J _C–F = 3.3 Hz), 123.6, 115.3 (d, J _C–F = 21.3 Hz), 108.7, 107.8, 34.9. IR (KBr, plate): ν = 3429, 2950, 2923, 1719, 1609, 1494, 1437, 1279, 859, 779, 705 cm^–1. ESI-HRMS: m/z calcd for C₁₁H₁₁FN [M + H]⁺: 176.0876; found: 176.0866.1-Methyl-2-(2-Fluorophenyl)-1H-pyrrole (3c)Compound 3c was obtained following the method A. Colorless oil; R_f  = 0.2 (PE–CH₂Cl₂ = 20:1); yield 91% (64 mg). ¹H NMR (400 MHz, CDCl₃): δ = 7.38–7.32 (m, 2 H), 7.19–7.12 (m, 2 H), 6.78 (t, J = 2.0 Hz, 1 H), 6.25 (d, J = 2.0 Hz, 2 H), 3.58 (s, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 160.0 (d, J _C–F = 245.0 Hz), 132.1 (d, J _C–F = 3.1 Hz), 129.2 (d, J _C–F = 8.1 Hz), 128.2, 124.1 (d, J _C–F = 3.4 Hz), 123.5, 121.2 (d, J _C–F = 15.3 Hz), 115.7 (d, J _C–F = 22.5 Hz), 109.9, 107.9, 34.7. ESI-HRMS: m/z calcd for C₁₁H₁₁FN [M + H]⁺: 176.0876; found: 176.0871.